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groups of isopropyl), a second doublet a t 8.06 r (CHBattached to a double bond) a quartet a t 4.00 r (single proton attached to olefin); the single proton of the middle carbon of isopropyl a t 5.69 r and the aromatic protons a t 2.61 r. The fully saturated 2-imidazolidone V is obtained on hydrogenating I11 with platinum oxide in acetic acid as small colorless granules, m.p. 67.8-68.2’. Anal. Calcd. for C13HlaC12N20:C, 34.50; H, 5.58; C1, 24.75; N, 9.77. Found: C, 54.10; H , 5.62; C1, 24.80; N, 9.40. The infrared spectrum no longer shows the C=C band a t 6.15 p V is identified unequivocally by synthesis with the urea IV. I V is prepared following conventional procedures : 2-propanolamine + isopropyl-2-hydroxypropylamine isopropyl-2-chloropropylamine IV. IV is cyclized by treatment with sodium hydroxide in acetone to V, m.p. 67.768.2’. Mixed m.p. with hydrogenated 111, (IV)
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is not depressed and infrared spectra are identical. AI1 eIementa1 analyses are correct as required by theory. The results of our investigation indicate that cyclization will occur with propynyl ureas of the R
H
type -NCON
/
When R = H, the
\
\
CH~CECH parent urea is regenerated on treatment with water or base presumably through formation of a carbodiimide. The reaction offers a simple and facile route to 1,3-disubstituted imidazolones. A discussion of the mechanism and scope of the reaction will be published shortly. AGRICULTURAL RESEARCH DEPARTMENT AGRICULTURAL CHEMICALS DIVISION P. J. STOFFEL MONSANTO CHEMICAL COMPASY A. J. SPEZIALE ST. LOUIS66, MISSOCRI ItECEIVED DECEMBER 7, 1961
BOOK REVIEWS Azo and Diazo Chemistry.
Aliphatic and Aromatic Compounds. By HEINRICHZOLLINGER,Professor in the Eigenossische Technische Hochschule, Zurich, Switzerland. Translated by HARRYE. NURSTEN,Lecturer in the University of Leeds, Great Britain. Interscience Publishers, Inc , 250 Fifth Avenue, New York 1, N. Y. 1961. 444 pp. 17.5 X 24.5 cm. Price, $16.50. This book bears a close relationship to the Germanlanguage book by the same author, “Chemie der Azofarbstoffe,” Birkhauser Verlag, Basel, Switzerland, 1958; but the relationship is not the simple one of translation from German t o English, or even of second edition to f i s t with translation as an extra flourish. “Chemie der Azofarbstoffe” dealt exclusively with the chemistry of aromatic diazonium and azo compounds. Throughout, its point-of-view was that of reaction mechanisms and physical chemistry as it treated the major phenomena of interest t o the organic chemist or the dyeworks chemist dealing with these compounds. Important aspects of the dyeing process received their share of attention. About three-quarters of the content of the original book has been transferred, with modifications to keep it up-todate and with translation, to form the main substance of “Azo and Diazo Chemistry.” Those chapters devoted to technical aspects of azo dyes and dyeing were not carried over. In the new book their place, so to speak, is taken by several chapters or sections on aliphatic azo compounds which, altogether, comprise about a quarter of the work. The new book is about 307’ longer than its predecessor. Professor Zollinger writes of aromatic diazonium and azo chemistry with the confidence and command that one would expect from the world’s leading investigator in that area. Though respectful of the worthwhile contributions of earlier decades, he discards much of the older systematization and nomenclature in favor of a presentation organized largely according to the precepts of modern physical organic chemistry. His lucid presentation clears away the clutter of outmoded views which had made the area of pure chemistry to which azo dye technology is related as unfashionable as Whist. The many fascinating phenomena and challenging problems which Zollinger has revealed offer a stirring cqiportui~ity10 1 he iiivestigator willing to suffer the slights
of the style-conscious for the rewards of discovery in an exciting but neglected field. In presenting aliphatic azo chemistry, Zollinger is more the competent critic than the practicing master. Nevertheless, what he writes is authoritative and valuable. I t is inevitable that any general treatment of a fastmoving field should be partially out of F t e on the day of publication. The absence of Schmitz work on cyclodiazomethane and of Huisgen’s interpretation of the cycloaddition of diazomethane to olefinic bonds (as a concerted 1,3-dipolar addition) are cases in point. The translation from German into English seems faithful. Indeed, it is occasionally too much so. Traces of German word order or idiom now and t.hen show through. The book is beautifully printed and produced, atid errors are not obvious. However, the reviewer got a bit of peevish satisfaction out of seeing ( p , 409) Burnett misspelled “Bunnet” for a change. METCALF CHEMICAL LABORATORIZS BROWN UNIVERSITY JOSEPH F. BUNNETT ISLASD PROVIDENCE 12, RHODE Industrial Organic Nitrogen Compounds, ACS Monograph No. 150. By MELVIKJ. ASTLE, Professor of Organic Chemistry, Case Institute of Technology, Cleveland, Ohio. Reinhold Publishing Corporation, 430 Park Avenue, New York 22, N. Y. 1961. vii 392 pp. 16 X 23.5 cm. Price, $14.00.
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“This book has been writtetl in an attempt to summarize the chemistry of most of the types of organic nitrogen compounds. No single book has appeared in recent years which has accomplished this goal. Many very excellent treatises are available describing the chemistry of amino acids and proteins, alkaloids and heterocyclic nitrogen compounds. Accordingly these compounds are not discussed extensively in this monograph. In order to present a comprehensive survey of nitrogen chemistry it has been necessary to discuss the simple heterocyclic nitrogen ring systems in some defFil. Considerablc attentior1 has been given to the patetlt litcraturc in ordcr t u prcscnt dcvclolm~cntsfrom thc iudus-
Feb. 5, 1962
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trial laboratories as well as those from other institutions. tive survey integrating a variety of crystallographic fields. Reaction mechanisms are discussed whenever they appear He succeeded in providing an interesting and intelligent useful in understanding the chemistry involved but no at- introduction suitable for readers with diverse backgrounds. The organization was such that he was able to bring the tempt is made to make this work an approach to the theory of work up to date in the recent Second Edition by making reactions. ” The above quotation from Professor Astle’s Preface ex- minor revisions and modest additions. plains quite well the purpose and scope of this .4CS MonoThe most striking feature of this book is the lack of the graph. Generally speaking, perusal of the book indicates formal mathematical development so characteristic of other that the author has done an excellent job within the frame- books in this field. Indeed, one is led to feel that those few mathematical formulas which do appear were recorded work he has set for himself. The book should find w-ide value as a quick reference tool, reluctantly for the want of a better mode of expression. not only in industrial research organizations but in academic The burden of each argument therefore falls upon exposition institutions as well. It probably will be of greatest use to and, fortunately, this is the strong point of the book. The persons not expert in the chemistry and technology of or- author writes with charm and style and, in an unhurried ganic nitrogen compounds who from time to time need way, carefully builds each argument with the aid of nuauthoritative and up-to-date answers to specific questions. merous examples and excellent illustrations. For this reason, By the same token, it will surely be a worthwhile addition many students encountering crystallography for the first to the bookshelf of the research chemist who has frequent time have found this book a useful adjunct to more formal occasion to work with nitrogen derivatives yet is not a pri- presentations. mary investigator in the field. The first part of the book is concerned with the identificaAs one might expect, the author has organized his subject tion of crystalline substances. Crystal morphology and matter according to functional classes. Chapter headings symmetry are treated a t length to provide the basis for are as follows: 1, Aliphatic Amines, 2, Arylamines, 3, later discussions of identification procedures involving Heterocyclic Amines, 4, Hydrazines, Azo Compounds, Di- crystal optics and X-ray powder diffraction analysis. azonium Salts, and Oximes, 5, Nitriles, Amides and Amino The second, and larger, part of the book deals with crystal Acids, 6, Isocyanates, Ureas, Thioureas, 7, Aromatic Nitro structure analysis. The geometric principles involved in and Nitroso Compounds, 8, Aliphatic Nitro Compounds. the determination of unit cells are treated in terms of the For each class of compound, the discussion covers ( a ) gen- reciprocal lattice for a variety of experimental methods. eral properties and characteristics, (b) methods of prepara- This is followed by a short treatment of the relationship of tion, (c) reactions and ( d ) industrial utilization. A list of structure to diffraction intensities and the determination references to literature and patents is appended to each and use of space group symmetry. A number of well chosen chapter. examples of structure determinations are then discussed in Emphasis is on the chemistry of organic nitrogen com- detail to illustrate the principles involved in trial and error pounds rather than on commercial aspects. This is as it methods. should be, nevertheless trade names and approximate The last two chapters have been considerably expanded production figures for important products are mentioned, in this new edition. The first of these provides an introducand the references, which appear to have been carefully tion to modern methods of structure determination and reselected, include many patents. Most of the references finement. A variety of Fourier syntheses, vector syncarry dates within the past two decades up to and including theses, Fourier transforms and statistical intensity relation1958. ships are qualitatively discussed and illustrated with exIn discussing methods of preparation and reactions of a amples. The last chapter briefly notes the effects of crystal given class, the author gives a good deal of moderately de- size, texture and disorder on diffraction intensities. tailed information, e g., yields, melting and boiling points, OF CHEMISTRY reaction conditions, work-up procedures, and so on. On DEPARTMENT ROBERT E. HUGHES OF PENNSYLVANIA UNIVERSITY occasion, brief discussions of reaction mechanisms are prePENNSYLVANIA sented. The result is a good compromise between breadth PHILADELPHIA, and depth, both from the standpoint of the laboratory chemist and from that of the research director. “Industrial Organic Nitrogen Compounds” is not a book Reference Electrodes. Theory and Practice. Edited by one can sit and read comfortably from cover to cover. Birkbeck College, London, and GEORGE DAVIDJ. G. IVES, I t is rather a ready reference volume packed with well J. JANZ,Rensselaer Polytechnic Institute, Troy, New chosen information which will provide partial, if not comYork. Academic Press Inc., 111Fifth Avenue, New York plete, answers to the questions most likely to be asked in this 3, N. Y. 1961. xi 651 pp. 16 X 23.5 cm. Price, area of science and technology. $20.00. CENTRAL RESEARCH DIVISION AMERICANCYANAMID COMPANY JOHN H. FLETCHER The title covers only a part of the contents of this book. I t is really a summary, in unsystematic form, of a large STAMFORD, CONNECTICUT part of electrochemistry. It will probably be of most use in directing research workers to the literature of the subChemical Crystallography. An Introduction to Optical and ject. In this respect it is admirable, as the authors have X-Ray Methods. Second Edition. By C. W. BUNX.. searched out even obscure references to the use and preparaOxford University Press, 417 Fifth Avenue, New York tion of the most utilized electrodes. However, the text will in many cases without resort to the original papers. 16, N. Y . 1961. xiii X 509 pp. 16.5 X 24 cm. Price, serve One criticism that can be made is that the authors ar,: $12.00. not clear as to what they mean by the term “electrode. When the first edition of this book appeared in 1945, the It appears as metal-electrolyte, as in most galvanic cells; a\ semiconductor-electrolyte when utilizing glass surfaces: as field of X-ray crystallography was expanding rapidly both in this country and abroad. Textbooks were needed to link membrane surface-electrolyte; and as liquid-liquid junctions in most of the biological applications. It is probably only the ancient subjects of crystal morphology, lattice geometry in the last case that real misunderstandings can arise in and crystal chemistry with the theory and techniques of X-ray diffraction and crystal structure analysis. Treatises the interpretation of measurements, but such false interpretatious can occur particularly with data on colloidal were needed to develop systematically the formal theory and the experimental state of X-ray crystallography in materials. order to prepare the way for the rapid advances to come. The book should be especially useful to active workers in I n time even additional compendia would be required to electrochemistry and in fields utilizing electrochemical encompass the ever-growing literature. methods. The care that is necessary if precision is to be Among the many books written in the past twenty years obtained is emphasized and illustrated by excellent diagrams to meet these needs, “Chemical Crystallography” has oc- and illustrative data. I t should prevent novices from plungcupied a unique position. Neither a textbook nor a ing into research involving electrodes without realizing their treatise, the book has nevertheless maintained a substantial limitations, but this is probably too much to expect. following over the years because it merits so well its subThe reviewer is pleased to observe the rather belated title, “An Introduction to Optical and X-Ray Methods.” recognition in this volume of the utility of simple galvanic Tlie author undertook the difficulttask of writiiig a descrip- cells with oiic type of electrode its bourceb of precision
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